Insoluble azo compounds



Patented Mar. 29, 1938 I UNITED STATES 2.11am v msownm azo COMPOUNDS AMiles 'A. Dahlen, Frithjo! z wilgmeyer, Newell M.

Bigelow, and Robert F. Deese, Jr., Wilmingto DeL, assignors to E. I. duPont de Nemours a:

Company, Wilmington, DeL,

Delaware a corporation of No Drawing. Application September 20, 1934Serial No. 744,786

b 23 (llaims.

, This invention relates to azo dyes, to a method 01 making azo dyes, toa process dyeing a material with an azo dye, andto a material dyed withan azo dye. K

The azo dyes are a well-defined group containing the chromophor --N=N-.The chromogen of azo dyestuffs comprises two aryl radicals with thechromophor between them. The mono azo dyes are generally prepared byjoining two components of which the first, an amine, is called the azocomponent, and the second, usually a phenol, an amine, or an activemethylene compound is called the coupling component. In coupling thecomponents, the azo component imdiazotized in a manner which will beunderstood by persons skilled in the art, and is reacted with the secondcomponent, often in solution. Generally speaking, the aryl nuclei of theazo dyes contain certain substituents which change, but do not origiognized class, divided into two groups, of which the one tends to makethe dyestuff water-soluble, and the other does not. In this inventionthose auxochrome groups which tend to make the dyestufl water-solubleare called s-auxochromes and those which do not are calledn-auxochro'mes.

The prior art azo dyes are applied to fabrics, or to other materials tobe dyed, in three general ways: (a) The dyestufl is dissolved ordispersed in a suitable bath and the material is dipped in the bath. Tobe used in this manner the completed m'estuff must be substantive to thematerial which is to be dyed. (b) A substantive coupling component isdirectly afllxed to the fabric, which is then treated with thediazotized component, completing the dye on the material. (0

A substantive azo component is directly affixed to the fabric which,treated with the coupling component, completes the dye on the material.

I The term substantive means that the dye or the particular componenthas substantial aflinity for the materialfrom aqueous solution orsuspension. So far as we areaware no instances are recorded ofa-materlal having been dyed with an azo color of which none of the azo,nor the coupling component, nor the complete color were substantive.

. It is an .object of this invention to dye a ma- I terial with an azodye of which neither the azo component, the coupling component, nor thecompleted dye is substantive. Another object of the invention is toproduce a material dyed with a dyestufi of which neither the azocomponent, the coupling component, nor the finished dyestufi issubstantive. Another object of .the'invention is to produce superioryellow dyestuffs: It is also an object of this invention to produce azocolors useful-as pigments. Other objects of the invention will be inpart apparent and in part her'einafter set forth. I

' selves.

(o a-s) The objects of the invention are accomplished,

generally speaking, by impregnating the material to be dyed with anon-substantive azo component and a non-substantive coupling comcallyspeaking, by impregnating a fabric, 'or material to be dyed, with apaste containing a nonsubstantive,- n-auxochrome-substituted,.diazotized arylamine stabilized by conversion to a water soluble diazoamino derivative, and a non-substantive aceto-acetyl-arylide which maybe nauxochrome substituted, and by exposing the impregnated material atelevated temperature tothe action of a weak acid. i In the practice ofour invention, as a first component we may use any non-substantive,n-auxochrome-substituted, diazotized aniline. It is also possible to useunsubstituted diazotized aniline as the first component, but thedyestuffs produced by the use of an nauxochrome-substituted', diazotizedaniline are superior to the extent that they constitute an invention inthem- Exemplary of the very large number of compounds which can be used,when diazotized, as the azo component are the following: 2-methoxy-naphthylamine; 2-methoxy-ani1ine; 2- phenoxy-aniline;2-ethoxy-aniline; 2-chlor-5- methyl-aniline; 2-methyl-aniline;2-methoxy-5- methyl-aniline; 2-methoxy-4-chlor 5 methylaniline;2:5-dimethoxy-aniline; 2:5-diethoxyaniline;2:5-dimethoxy-4-chlor-aniline; 5-brom- 2-methoxy-aniline;3-iodo-6-methoxy-aniline; 3-

. iodo-6-ethoxy-aniline; 3-methyl-4-chlor-aniline;

3-brom-6-ethoxy aniline; 3-chlor-6-ethoxy-an'iline; 3-ethoxy aniline;3-phenoxy aniline; 3

line; 3-chlor-6-methyl-aniline; 3-methyl-aniline;-

3-brom-5-methyl-aniline; 3-chlor 6 phenoxyaniline;2:5-dimethyl-4-chlor-aniline;' 4-ethylaniline; 4 benzo trifluor aniline;4 chlor-2- methoxy-aniline; .4-brom-2-methoxy-aniline; 4-brom-2-ethoxy-aniline; 4 iodo-2-methoxyg-aniline; 4-methoxy aniline;4-chlor-2-ethoxy-aniline; 4-phenoxy aniline; 4-ethoxy aniline; 4-brom-2ephenoxy aniline; 4 methoxy-Z-chloraniline; 4-ch1or-2-methylaniline; 4-methyl-3- brom aniline; 4 brom 3 methyl aniline; 4- methyl--3 chlor aniline; 4-methyl aniline; 4- chlor-2z5-dimethyl aniline;4'-chlor-2-phenoxyaniline; 4-methoxy-3-chlor aniline; 4-phenoxy-2-chlor-aniline; 4-chlor-2:S-diethoxy-aniline; 3- ethoxy aniline;3-methoxy aniline; 3 methylaniline; 3 chlor 2 methyl-aniline; 3-chlor-2-methoxy aniline; 2-ethox'y aniline; 2-methoxy- 70 thylamine.

aniline; vB-mathyl anilirne; alpha-naphthylamine; beta-naphthylamine.

In. the practice of the preferred form ofthe invention the azocomponent, diasotized, is coupled with a stabilizing agent z Forinstance, it is Joined by the azo'group to the nitrogen group ofpiperidine. 'carboxylic acid. After stabilization this component can bemixed with the coupling component without reaction provided the mixtureis alkaline. The presence of an acid medium would break up thestabilized am component, which would immediately react with thecouplingcomponent to form the complete color.

A great variety of compounds maybe used as the coupling component. Thiscouplin'gcomponent, broadly speaking, is an aceto-acetyl arylide havingan aryl nucleus that may or may not have an n-auxochrome substituent.Although.

several instances are given hereinafter in which there are no'substituents in the second aryl nucleus, the presence of substituentsis frequently desirable. Among the coupling components whose use hasbeen found satisfactory are the aceto-acetyl derivatives of thefollowing: 2- brom-4-methyl-aniline; '2-chlor-4-ethyl-anlline;

2'-chlor+4-phenoxy-aniline; 2-chlor 4,- ethoxye -2 5-dimethoxy-aniiine;

aniline; 2 ethoxy-aniline; 2 methoxy-i-naphthyla'mine; 2-methyl-aniline;2-methoxy 4 chlor-S-methyl-aniline;

line; 2-methoxy-5-brom-aniline; 2-methoxyaniline; 2-phenoxy-aniline:2-methoxy-5-meth- 3-methoxy-l-naphthylamine: s brom-1-naph-. thylamine;3-chlor-6-methoxy-aniline; 3-chlor-' 6-phenoxy-anlline;S-methoxy-aniline; 3-chlor- 1 aniline; 3-brom-6-methyl-aniline;3-ethoxy-aniline; 3-methoxy-4-chlor-aniline; 3-methoxy-4- brom-aniline;3-etho'xy-4 chlor-aniline; 3-methoxy-5-chlor-anilineS-methoxy-b-brom-aniline 3-methoxy-4-methyl-B-chlor-aniline;3-phenoxyaniline; 3-cyclohexyl-aniline; 3-benzyloxy-aniline .35-dimethoxy-aniline; chlor-aniline; 3 5-diethoxyaniline; 3:5-dimethyl-anlline; 4-methoxy-l-naphthylamine; 4-methyll-naphthylamine;4-methyl-2-naphthylamine; 4-ethoxy-aniline; 4-methyL-5-chlor-anili'ne;-4- chlor 6 methon-anillne; 4-metlrvl-aniline; 4- brom-G-ethoxy-aniline;4 methyl 5 brom-aniline; 4-phenyl-aniliner 4-phenoxy-aniline; 4-methoxy-aniline; 4-chlor-7-naphthylamine: 4-

benzyloxy-aniline; fi-rnethoxy-l-naphthyl'amine;

5-chlor-1-naphthylamine; 5-'chlor-7-naphthylamine;5-chlor-6-methyl-aniline; 5-chlor-6- methoxy-aniline:7-chlor-l-naphthylamine; 4- chlor-anillne; alpha-naphthylamine;beta-naph- Although a large number of coupling components have beenrecited herein. it is to be understood that they are not exclusive ofothers, and that the other components falling within the broad claimsmay also! used.

2-ethoxy-4-chlor-ani- 3:5-dimethoxy-4- In the form of the inventionwhich involves the dyeing of a cloth by the so-called process of print-,

ing. the azo component, diazotized and stabilized as hereinabovedescribed, is mixed in a basic paste with the second component, and thepaste is-applied to an etched or printing"'roller which impregnates thefabric by'contact. The fabric may then be placed in a-closed containerto be subjected for a few seconds at elevated temperature to the actionof the fumes-of an acid, usually in the presence of water vapor. Theacid used may conveniently be acetic acid. The acid neutralizes thebasi'city of the paste, the complex with the stabilizing agent, such asthe piperidinealpha-carboxylic acid complex is broken up, thefirst-component is freed, and couples with the coupling component. Itisour surprising dis-- covery that by this method azo colors which couldnot be used for dyeing because neither the azo component, the couplingcomponent, nor the dye itself were substantive can be used to colorfibres and other dyeable materials and produce a superior dyeing. Thesedyes may advantageously include as substituents in the aryl nuclei, annauxochrome. The n-auxochromes are, specifically, the groups alkyl,alkoxy. halogen, aryloxy, aralkyl, aralkoxy, aryl, hydroaryloxy, andtrin-auxochromes are also satisfactory substituents in the aryl nucleusof the coupling component.

Generally speaking. entirely satis- However, coupling components havingno nauxochrome substituents generally may be made to produce excellentcolors; and, consequently, the number of n-auxochrome substituentsin thecoupling component, even in the preferred form of the invention, variesfrom zero to the limit of its capacity. However, the addition of largenumbers of substituents to the aryl nucleus of the coupling component.while possessing no disadvantages, does not appear to have distinct ad-.

vantage over similar compounds containing a fewer number ofsubstituents.

The following examples are illustrative invention:

Example 1 A printing paste was prepared according to the formula:

of the tained by the action of diazotiaed- 2 D parts of starch-gumtragacanth thickener.

prepared according to the following formula:

parts of wheat starch 360 parts of a 5% solution of gum tragacanth 560parts of water 36.0 parts of water at I".

100.0 arts total.

Cotton goods were printed from an engraved copper roll with the abovepaste, dried and then exposedfor 1% minutes to the vapors of a boiling5% solution ofacetic acid. The printed cotton was then rinsed withwater,soaped 1 minute at 160 F. in soap solution, rinsed again anddried. The treated fiber was colored bright yellow by a dye of theprobable formula:

| ENG-0 can 0] The dye had excellent fastness to light, chlorine, andlaundering.

Example 2 printing paste was prepared according to the followingformula: i

100.0 arts Cotton goods were printed with the above paste from anengraved copper roll and dried. The cloth'was then exposed forgl minutesto a 5% acetic acid ager, rinsed, soaped for 1 minute to remove thecarboxylic acid at 160 F. in soap solution,vand dried. The printedportions of the goods were dyed a bright greenish yellow by thedeveloped dyestuil of the probable formula:

. The dyeings showed excellent fastness to light,

chlorine, and laundering.

lt'xample .3

A printing paste was prepared according to the following formula:

3.5 parts of the diazoimino compound obtained by the reaction ofdiazotized 3 chlor-' G-methoxy-aniline with piperidinealpha-carboxylicacid."

2.5 parts of aceto-acetyl-lnaphthylamide 6.0 parts of cellosolve 2.0parts of a 26% solution of sodium hydroxide 50.0 parts of starch-gumtragacanth thickener 36.0 partsof water at F.

100.0 parts Cotton goods were printed from an engraved copper roll withthe above paste, and then dried. The printe'dcotton was exposed for lyminutes to the vapors of a boiling 5% solution of acetic acid; it wasnext rinsed, soaped 1 minute at .160

F. in soap solution, rinsed. and dried. The.

laundering.

sodium hydroxide .100. 0 parts treated fiber was colored a reddishyellow by a dyestufl of the probable formula:

i OCH cook.

N=N-C com:

The dyeings possessed a satisfactory degree of resistance to the actionof light, chlorine, and

Example 4 A printing paste was prepared according to the followingformula: i

3.5 parts of the diazoimino compound obtained by the reaction ofdiazotized 5-chlor- Z-methyl-aniline withpiperidinealpha-carboxylic-acid 2.5 parts ofaceto-acetyl-alpha-naphthylamide 6.0 parts of cellosolve 2.0 parts of a26% solution of sodium hydroxide 50.0 parts of starch-gum tragacanththickener 36.0 parts of water at 140 F.

100.0 parts Cotton goods were printed with the above paste from anengraved copper roll, and then dried. The cloth was next aged for 1minutes in a 5% acetic acid ager, rinsed, soaped for one minute at F.insoap solution, rinsed again and dried. The treated portions of the clothwere colored a reddish yellow by the dyestufi of the probable formula:

I C O CH:

The dyeings showed a satisfactory degree of resistance to light,chlorine, and laundering.

.Exdmple 5 A printing paste was prepared according to the formula:

3. 5 parts of the diazoimino compound prepared by the reaction ofdiazotized CONH 5 -'chlor 6 methyl-aniline with I 2. v5 parts of acetoacetyl alpha naphthyl amide I 6.0 parts of cellosolve 2.0 parts of a 26%solution of droxide 50. 0 parts or starch-gum-tragacanth thickener 36. 0parts of water at 140 F.

Cotton goods were printed with the above pafie from an engraved coppervroll, and dried. The cloth was then aged for 1 minutes in a 5% aceticacid ager, rinsed, soaped for one minute-at 160 F. in soap solution,rinsed again and sodium hyplperidine alphacarboxylic-acid 1 dried. Theprinted portions or the goodsf were 5;

dyed a reddish yellow by adyestuif of the probable formula:

C1 OH: COCH:

5 I p N=NCH CONE The dyeings possessed a fair degree of fastness tolight, chlorine, and laundering.

Example 6 A printing paste was prepared according to the followingformula: I

3.5 parts of the diazoimino compound derived 3-chlor-6-methoxy anilinewith piperidine-alpha-carboxylic-acid of aceto-acetyl-beta-naphthylamideof cellosolve of a 26% solution of sodiunwhydroxide ofstarch-gum-tragacanth thickener parts of water at 140 1".

100. parts Cotton goods were printed from an engraved copper roll withthis paste, and dried. They were then exposed for one minute to a aceticacid a'ger, rinsed, soaped at the boil for one minute with al% soapsolution, rinsed and dried. The printed portions of the goods werecolored a yellow by the dyestuff of the probable formula:

- coon;

The dyeings showed excellent fastness to launder- I lug-and to theaction of light and chlorine.

Example 7 prepared according to A printing paste was the followingformula:

i00.0'parts' Cotton goods were printed from an engraved copper roll withthis paste, and were dried. The goods were then exposed to a 5% aceticacid ager at the boil, rinsed, soaped at the boil for one minute with a1% soap solution. and-rinsed again. like printed portions ofthegoodswere colored a sodium hyfrom the reaction of diazotized reddishyellow by the dyestuif of the probable formula:

- 7 00cm N= N bn com:

OCH:

The dye has an excellent resistance to laundering, and to the action oflight and chlorine.

Example 8 The substitution of 3.2 parts of the diazoimino compoundprepared by the reaction of diazotised 5-chlor-2-methyl-aniline andpiperidine-alphacarboxylic-acid and 2.8 parts of aceto-acetyl-7-methoxy-l-naphthylamide for the color components given in Example 7gives a printing paste which, when printed and developed in'the usual.manner gives reddish yellow dyeings of satisfactory resistance tolight, chlorine, and laundering. The probable constitution of thedyestuif may be represented by the formula:

CH: COCH:

N=N-CH a Q 0.01m Cl 1- a EmampleQ The substitution of 3.2 parts of thediazoimino compound prepared bythe reaction of diazotized5-ch1or-6-methyl-aniline with piperidine-alphacarboxylic-acid and 2.81parts of aceto -acetyl-'l-- methoxy-l-naphthylamide gives a printingpaste which dyes cotton or regenerated cellulose a reddish yellow. Thedyestufl shows a satisfactory degree of resistance to the action oflight, chlorine, and laundering. The probable composition of thedyestuil' is represented by the formula:

$1 ICH:

COCHI CONH Example 10 A printing paste was prepared according to theformula:

3.5 parts of the diazoimino compound derived from the reaction betweendiazotized 3-chlor-6-methoxy-aniline and piperidine-alpha-carboxylicacid i 2.5 parts of aceto-acetyi-2-methoxy-1-naphthylamide Y 6.0 partsof cellosolve' 2.0 parts of a 26% solution of sodium hydroxide 50.0parts of starch-gum-tragacanth thickener 36.0 parts of water at F.

100.0 parts chlorine, and Natal laundry test. The dye had Cotton goodsprinted with this paste an'd developed in the usual manner were dyed aweak yellow by developed dyestuil of the probable formula: V

OOHa' J CQCH1 OHIO The dyeing's were altered by the action of chicrine,and are probably of no commercial value.

Example 11 r A printing paste was prepared according to the followingformula:

3.6 parts of the diazoimino compound formed by the reaction ofdiazotized 4- chlor-fi-ethoxy-aniline with piperidine-alpha-carboxylicacid in an alkaline solution 2.4 parts of aceto-acctyl-4-ethoxy-anilide,

6.0 parts of cellosolve 2.0 parts oi 26% sodium hydroxide solution 50.0parts 01' starch-gum-tragacanth thickener 6.0.parts oi water at 140 F.

100.0 parts Cotton goods were printed from an engraved copper roll withthe above paste, dried, and then aged for 1% minutes in a 5% acetic acidager, rinsedwith water, soaped for 1 minute at 160 F. in /2% soapsolution, rinsed and dried. The printed portions of the cotton goodswere dyed a bright yellow by the dye of the probable formula:

l H-N-O-O 0.11;

The dye possessed good fastness to light, chlorine, and Naial laundrytest.

Example 12 A printing paste was prepared according to the followingIormula:

100.0 parts Cotton goods were printed, aged and soaped according toprocedure given in previous examples. The resulting prints were brightgreenish-yellow and showed good iastness. to light,

the formula:

Example 13 A printing paste was prepared according to the followingformula:

3.5 parts of diazoimino compound formed by 15 the reaction of diazotizedi-chlor- G-methoxy-aniline with 'pi'peridinealpha-carboxylic-acid 2.5parts of aceto-acetyl-4-ethoxy-aniline 6.0 parts of ceilosolve 2.0 partsof 26% sodium hydroxide solution 50.0 parts of starch-gum-tragacanththickener 36.0 parts of water at 140 F.

100.! parts Cotton goods were printed, aged, and soaped according toprocedure given in previous exampics.

The resulting prints were bright yellow and showed good iastness tolight, chlorine, and 30 Natal laundry test. The dye had the formula:

COCH:

Example 14 A printing paste was prepared according to the followingformula:

3.6 parts of, the diazoimino compound formed by the reaction ofdiazotized'3-ehlor 45 6-ethoxy-aniline withpiperidine-alpha-carboxylicracid in an alkaline solution 2.4 parts ofaceto-acetyl-4 6.0 parts of ceilosolve 2.0 partso'f 26% sodium hydroxidesolution 50.0 parts of starch-gum-tragacanth thickener 36.0 parts ofwater at -ethoxy-aniline Cotton goods were printed, aged, and soapedaccording to procedure given in previous examples. The resulting printswere bright yellow and showed very good iastness to light, chlorine, andNafal laundry test. The probable formula i'or the dye was:

C OOH:

. A printing 'paste was prepared according to the following formula:

n-rLO-oom Example 15 chlorine, and Nafal laundry test.

3.7 parts of the diazoimino compound formed'by the reaction betweendiazotized 3- brom-6-methoxy-aniline andpiperidine-alpha-carboxylic-acid in an alkaline solution 2.3 parts ofaceto-acetyl-4-ethoxy-aniline 6.0 parts of cellosolve 2.0 parts of 26%sodium hydroxide solution 50.0 parts of starch-gum-tragacanth thickener36.0parts-of water at F.

100.0 parts Cotton goods were printed. aged, and soaped according toprocedure given in previous examples. The resulting prints were brightyellow and showed very good fastness to light. chlorine, andNafallaundry test. The probable formula for the dye was:

OH: O

100.0 parts Cotton goods were printed, aged. and soaped according toprocedure given in previous examples. The resulting prints were brightgreenish-yellow, and showed very good fastness to light.

The probable formula for the dye was:

CHI 0 Example 17 A printing paste was prepared according to thefollowing formula:

3.3 parts of diazoimino compound (formula same as in Example 18) madefrom diazotized ortho methoxy-aniline and piperidine alpha carboxylicacid, I 2.7 parts'of aceto acetyl 3- chlor-6-methoxyaniline 6.0 parts ofcellosolve K 2.0 parts of 26% sodium hydroxidesolution 50,0 parts ofstarch-gum-tragacanth thickener 36,0;parts of water at 140 F.

100.0 parts Cotton goods were printed, aged, and soaped. according toprocedure given in previous examples. The resulting prints werebright-greenish-yellow and showed good fastness to light, 5

chlorine, and Nafal laundry test. The probable formula for the dye was:1

Example 18 A printing paste was made according to the folldwing formula:

3.4 parts of the diazoimino compound formed by thereaction of diazotizedorthoethoxy-aniline with piperidine-- 'alpha-carboxylic-acid in analkaline solution aceto-acetyl S-chlor 6 methoxyaniline 6.0 parts ofcellosolve Q 2.0 parts of 26% sodium hydroxide solution 50.0 parts ofstarch-gum-tragacanth thickener 36.0 parts of water at 140 1".

2.6 parts of 100.0 parts Cotton goods were printed, aged, and soapedaccording to the procedure given in previous examples. The resultingprints were dull yellow and'only showed fair fastness to chlorine.light. and Nafal laundry test. The probableformula for the dye was:

ClHl o N=Non O a o J v is? I I CH:

Example 19 A printing paste was prepared according the followingformula:

3.6 parts'of the diazoimino compound formed by the reaction betweendiazotized] 3-,chlor-6-methoxy-aniline andpiperidine-alpha-carboxylic-acid 2.4 parts ofaceto-acetyl-m-methoxy-aniline 6.0 parts of eellosolve V 2.0 parts of a26% solution of sodiumhydroxide 50.0 parts of starch-gum-tragacanththickener 36.0 parts of water at 140 1".

100.0 parts Y Cotton goods were printed with this paste from an engravedcopper roller, and then dried. The

goods were next aged for 1% minutes ins 5% acetic acid ager, rinsed,soapedf or one minute at F. in V27, soap solution, rinsed. and dried.The printed portions of the goods were dyed a bright yellow by adyestui! of the probable formula:

OCH:

COCH:

N=N-OE comer born The dyeings possessed a good degree of stability tolight, chlorine and laundering.

Example A printing paste was prepared according to the I followingtormula:

20 3.5 parts. or the diazoimino compound derived from the reaction ofdiazotized 3- chlor-B-methoxy-aniline withpiperidine-alpha-carboxylic-acid' 2.5 parts ofaceto-acetyl-m-ethoxy-aniline 8.0 parts of cellosolve 2.0 parts of 2.26%solution of sodium hydrox- Y ide 50.0 parts of starch-gum-tragacanththickener 38.0 parts of water at 140 F.

. 100.0 parts Cotton goods were printed with the above paste, and thendried. The goods were then exposed for 1% minutes to the vapors of aboiling 5% solution of acetic acid, rinsed, soaped for 1 minute at 160F. in soap solution, rinsed, and dried. The printed portions or thegoods were dyed a bright greenish yellow by the dyestufl ot the probableformula:

can

'lhe dyeings possessed a very'satisi'actory degree of fastness to light,chlorine, and laundering.

" Example 21 A printing paste was prepared according to the lollowingformula:

3.0 parts 01 the diaaoimino compound obtained s by the action ofdlazotized 3-chloralpha-carboxylic-acid 2.2 parts oraceto-acetyl-o-methyl-aniline 6.0 parts 01' cellosolve 2.0 parts 01 26%sodium hydroxide solution 50.0 parts of starch-gum-tragacanth thickener30.0 parts ot'water at 140 F.

100.0 parts Cotton goods were printed from an engraved copper roll withthe above paste, and then dried. The printed cotton was exposed for 1%minutes to the vapors of a boiling 5% solution of acetic 7 acid: it wasthen rinsed, soaped 1 minute at 160 B-methoxy-aniline on piperidine F.in soap solutionirinsed, and dried. The

treated flber was colored a greenish-yellow by a dyestufl of theprobabletormula:

The dye possessed a fair degreev of tastness to light, chlorine, andNatal laundry test.

' Example 22 A printing paste was prepared according to the followingformula:

3.5 parts oi the dlazoimino compound formed by the reaction ofdiazotized .3

. chlor-fi methoxy-aniline with piperidine-alpha-carboxylic-acid 2.5parts of aceto-acetyl-2:5-dimethoxy-anill e 6.0 parts of cellosolve -2.0parts or a 26% solution oi. sodium hydroxide 50.0 parts 01'starch-gum-tragacanth thickener 36.0 parts of waterat It 100.0 parts l 1I Cotton goods were printed from an engraved copper roll with the. abovepaste, and then dried.

The goods were then aged for 1% minutes in a 5% acetic acid ager,rinsed, soaped, for 1 minute at F. in soap solution, rinsed, and dried.

The printed portions of the goods were dyed a bright yellow' by the,dyestufl 'ot the probable formula:

light and i'airly good 'fastness to chlorine and laundering.

. Example 23 A printing paste was prepared according .to the' followingformula:

100.0 parts Cotton goods were printed from an engraved copper rollerwith the above paste, and then dried. The goods were then aged for 1%min utes in a 5% acetic acid ager, rinsed, soaped for one minute at 160F. in soap solution, rinsed and dried. The printed portions of the goodsThe dyestufl possessed a very good iastness to were tinted a brilliantreddish yellow, the dyestufl having the probable formula:

/ OOH:

' COCH! 2} OOH: N=N- K ONE Cl Cl These dyeings possessed excellentstrength, shade, and fastness to light, chlorine, and Nai'allaundrytest.

Example 24 -A printing paste was prepared according to the followingformula:

100.0 parts Cotton goods were printed from an engraved copper rollerwith the above paste, and were then dried. The goods were then exposedfor 1% minutes to a 5% acetic acid ager, rinsed, soapeddor minute at 160F. in /2% soap solution, rinsed,

and dried. The treated portions of the goods were tinted abright'greenish yellow by the dyestui'! of the probable formula:

- COCK! 0 ClHl N=N- H ONE Cl CgHl The dyeings. were very satisfactory instrength,

shade, and fastness to light, chlorine, and the Natal laundry test. I

5 Example 25 A printing paste was prepared according to the followingformulaz 3.3 parts of the diaaoimino compound formed by the action 0!diazotized 3-chlor-' G-methoxy-aniline andpiperidinealpha-carboxylic-acid 2.7 ofaceto-acetyl-Q-methoxy-4-chflor-5- methyl-anilide 6.0 parts oiceliosolveq 2.0 parts of 26% sodium hydroxide solution 50.0 parts ofstarch-gum-tragacanth thickener 36.0 parts of water at 140 F.

100.0 parts Cotton goods were printed i'rornan engraved copper rollerwith the above paste, and then dried. The goods were aged 1% minutes ina 5% acetic acid ager, rinsed, soaped one minute at 160 F. in soapsolution, rinsed, and dried.

The printed portions of the goods were dyed a. bright reddish-yellow,excellent in shade,

' strength, and fastness to light, chlorine, and the mula:

Natal laundry test. The probable structure of s the dyestui! may beexpressed as follows:

OCH:

Example 26 'A printing paste wasprepared accordingto the followingformula: N

3.3 parts of the diazoimino compoundobtained by the reaction oi'diazotized 3- chlor-fi-methoxyraniline withpiperidine-alpha-carboxylic-acid 2.7 parts ofaceto-acetyl-2-ethoxy-4-chloranilide 6.0 parts of cellosolve 2.0 parts01' --a 26% solution of sodium hydroxide 500 parts ofstarch-gum-tragacanth thickener 36.0 parts of water at F.

100.0 parts Cotton goods were printed with this paste from an engravedcopper roll, and dried. The goods were then developed for 1% minutes ina 5% acetic acid ager, rinsed, soape'd for 1 minute at 180 F. in soapsolution. rinsed, and dried.' The printed portions of the cotton weredyed a bright greenish yellow by a dyestui'f of the probable I ormula:

OCH:

' COCK! The dyeings were excellent in respect to strengthj 1 F shade,and Iastness to light, chlorine, and the Natal laundry test.

Example 27 A printing paste was prepared according to the followingformula:

3.2 parts of the diazoimino compound obtained by the action ofdiazotized 3-chlor- 6-methoxy-aniline uponpiperidinealph'a-carboxylic-acid V 2.8 partsotaceto-acetyl-2-methoxy-5-bromanilide 6.0 parts of cellosolve 2.0 partsof 26% sodium hydroxide solution 50.0 parts ofstarch-gum-tragacanththickener 36.0 parts of water at 140 F.

100.0 parts Cotton goods were printed with this paste from an engravedcopper roller, and were then drled.. The goods were exposedto a 5%acetic acid ager for 1% minutes, rinsed, soaped at F. for 1 minute inV2%-soapso1ution, rinsed, and dried.

The printed portions of the cotton were dyed a bright yellow by thedyestufl of the probable tor- OCH:

The dyestufl possessed satisfactory strength, shade, and fastness tolight, chlorine, and the v Nafal laundry test.

Example 28 I A printing paste was prepared according to the followingformula:

3.4 parts of the diazoimino compound obtained by the reaction ofdiazotized 3- w chlor-6-methoxy-aniline withpiperidine-alpha-carboxylic-acid 2.6 parts ofaceto-acetyl-2z5-dichloraniline 0.0 parts'of cellosolve 2.0 parts of a26% solution of sodium hydroxide 50.0 parts of starch-gum-tragacanththickener 30.0 parts of water at 140 F.

243 100.0 parts Cotton goods were printed with the above paste from anengraved copper roll, and then dried. The printed cotton was exposed for1% minutes to the vapors of a boiling 5% solution of acetic acid;

it was next rinsed, soaped for 1 minute at 160 F.

in soap solution, rinsed, and dried. The treated fibre was colored areddish yellow by a dyestufl of the probable formula: i

The dyeings possessed a satisfactory degree of resistance to light,chlorine, and laundering tests. Example 29 I A printing paste wasprepared according to the following formula:

3.6 parts of the diazoimino compound ob tained by the reaction ofdiazotized 3-chlor-6-methoxy-ani1ine withpiperidine-alpha-carboxylic-acid 2.4 parts ofaceto-acetyl-Z-chlor-aniline 6.0 parts of cellosolve 2.0 parts of a26%solution of sodium hydroxide v 50.0 parts of starch-gum-tragacanththickener 36.0 parts of water at 140 F. 5 a

100.0 parts Coupling component to I derivative application of an acidmedium.

to light; the fifth column shows the fastness of The paste was printedupon cotton goods and was developed in an acid atmosphere. The cloth wasdyed a greenish yellow which showed good resistance to the action oflight, chlorine, and laundering. Its probable composition may be 5represented by the formula:

Example 30 C The color components given in Example 28 were replaced bythe following components: 3.2 parts of the pipecolinic acid derivativeof diazotized 3-chlor-6-methoxy-aniline; 2.8 parts of Iaceto-acetyi-z-methoxy 5 bromaniline. The printing paste was prepared,applied to cotton goods and developed inthe manner previously described.The resulting prints were greenish yellow in color, and of excellentfastness to light, chlorine, and laundering.

The foregoing examples have been given to indicate the wide applicationandpossibilities of the invention. Many of the examples are direct-, edto printing pastes because they offer an excellent manner of applyingthe dyestufl'. The dyestuft can be, made, however, by following thegeneral principle hereinbefore explained, but

' without making a printing paste, by impregnating the fabric with thetwoconstltuents in a basic medium and causing them to react by the f Inaddition to the compounds disclosed in the foregoing examples we havemade the dyestuffs set forth in the following table and have dyedmaterials with them. The first column. of the table shows the azocomponent of the dye; the second shows the coupling component; the thirdshows the color of the dye formed by the combination of the componentsof the first two columns; the fourth shows the fastness of the dye thedye to laundering (Nai'al label test); and

' the sixth column shows the fastness of the dye to the chlorine test.Each of these tests is standard and the nature thereof will beunderstood by persons skilled-in the art.

Color in the presence Asocomponsnt Oouplingoomponent Oolor m g?"Chlorine Aoeto-scetyl derivative 2:5-dimothoxy-4-chlor-aniline...-2-methyl-6-ohlor.aniline Reddish-yollow i-chlor-o-ethoxy-aniline -..-doGreenlsh-yellow d-brom-b-methyl-onilin do do a-chlor-dmothory-anilinoD-methoxy-aniline do Do i-methoxy-aniline Reddish-yellow Gfl-methyN-chlor-anllln fin Greenish-yellow S-chlor-d-methoxy-anlline.i-methory-d-brom-anlline. dn l-mlor-o-msthyl-anilino o Yellowish-greenS-ohlor-d-methosy-aniline. I-methoxy-i-chlor-anillna. Greenishsllow Dos-methoxy-t-chlor-snilinon Bright low.. Fbrom-i-methyl-snilim dn Greenis-yollow 2:6'dimethyl-4-chlor-anilino... .do Reddish-yellow -.-doI-methoxy-aniiine 2:5- dimethoxy -4 chlor- Excsllsnt..

e. Gresnish-ysllow ii-methox -aniline.... In 1 do flzo-dimeoxy-krhlor-snilinenn ml r L-hnwv..nln. d-chlor-o-rnethoxy-aniline .-.d.Oreenish-yellow do s-methoxy-iychlor-sniline n do Fair 0.Hthoxy-d-chlor-anilin 0 Excellent.. Excellent ichlor-o-methyl-anilin n n(In do 2-methoxy-5-methyl-aniline--.-. in 0 do achlor-o-methoxy-anillne8-msthoxy-4-ohlor-snlline Reddish-yellow Good Doo-chlor-4-meth0xy-sni1ine.. 'Greenish-yellow Excellent3-chlor-o-methyl-aniline.. ii-chlor-i-methox -aniline Brightgreenish-yellow.. Good a-chlor-o-methoxy-snilina flzb-dimothyl-sn linedo -.do

-Do fl-methoxy-o-rnethyl-aniline Greenish-yellow Fairbehlor-o-msthyl-anilino do do a chlor-o-msthoxy-aniline a-ethory-onilinoBright-goonish-yellom. Excellent d-brom-o-mstll yg-anllinei-ethoxy-aniline...

2 bgimethoxy-amiline n flzt-dimethyl-i-chlor-snilino. do Yellowa-chlcr-4-ethoxy-aniline- Gresnish-yellow I-methoxy-i-chlor-iidomethyl-aniline. I s-chlor-o-msthyl-aniline. do do lairs-cblor-o-methyl-sniline flzb-dimathoxy-i-chlor- Reddish-yellow Excellent" tchlor-o-msthyl-anilinslu do o n n1, Q-ohlor-d-msthoxy-anillnelzb-dlethoxy-aniline Greenish-yellow n Good Do. b-chloHi-methyl-anilino.do do n Excellent Excellent.

or-ohon-aniline" s-gbenoxy-anilineu. Reddish-ysllow l'air Fair Fair. 5Do.-. 4- yloxy-onilln Good.-; Good Good. 1

not as a limitation: sarcosine, ethyl-taurine,

proline, 4-sulto-2-amino-benzoic-acid, methylglucarnine. The use orstabilizers such as these for the preparation of water-soluble diazoamino compounds is well known in the art.

.If it is desired to prepare the color apart from a material, thepreparation can be carried out by dissolving orsuspending the couplingcomponent in an aqueous medium, adding the diazc solution 01' an acidbinding agent, such as sodium acetate, sodium bicarbonate, and sodiumcarbonate, or the like. The colors formed are insoluble in water, andare separated by precipitation and filtration.

e By this invention there may be produced yellow dyes which are ofoutstanding fsstness, some of which are actually superior to'vatdyes,and, of course, are much less costly. These dyes also constitute a greatadvance over the insoluble, yellow azo dyes known to the prior art,being superiorin this, particularly, that while retaining theinexpensive nature of other azo dyes, they attain the desirablequalities 'of greater permanence. Another advantage of the invention isthe discovery that non-substantive dyestufls whose use components andcoupling components are also not'substantive can be used for dyeing.Another advantage of the invention lies in the pigments which'may beformed by reacting the components in solution. It is not impossible thatsome of these colors may have been made before as p18- ments, however,to the best oi! om knowledg none of these colors has ever before. beenused as a dye. claimed only to the extent that they may be new.

I These dyestuii's are of major use in connection with cotton andregenerated cellulose, and are of minor application with wool, silk,cellulose esters and ethers, and. the like.

As many apparently widely diflerent embodiments of this invention may bemade without departing from the spirit and 'scope thereof, it is tobeunderstood that wedo not limit ourselves to the specific embodimentsthereof except as defined in theappended claims.

-We claim:

1. A textile fabric dyed with the coupling prodnot of a diazotiz'edaniline and a non-substantive aceto-acetyl anilide.

2. A cellulosic fabric dyed with the coupling product of anon-substantive, n auxochromesubstituted, diazotized aniline and anon-substan- Consequently, these pigments are tive, n auxochromesubstituted aceto acetyi anilide.

3. A cellulosic material colored with the coupling product 01' anon-substantive, diazotized aniline and a non-substantiveaceto-acetylanilide.

of the coupling component are halogen and alkoxy.

- a 6. A cellulosic material dyed with the coupling product of anon-substantive, n-auxochrome-substituted, diazotized aniline and anon-substantive,

nauxochrome-substituted. aceto-acetyl-anilide in which auxochromes ofthe diazo component I are halogen and alkoxy and in which auxochromes ofthe coupling component are halogen and alkoxy. P

7. A cellulosic material dyed with the coupling product or a nonsubstantive, n-auxochrome-substituted, diazotized aniline and anon-substantive, n-auxochrome-substituted aceto-acetyl-anilide in whichauxochromes or the diazo component are halogen and alkoxy andin whichthe auxochrom of the coupling component is alkoxy. w

8. A cellulosic material dyed with the coupling product of anon-substantive, n-auxochrome-substituted, diazotized aniline and anon-substantive, n-auxochrome-substituted aceto-acetyl-anilide in whichauxochromes oi the diazo component are halogen and alkoxy and in whichthe auxochrome of the coupling component is halogen.

9. A cellulosic fabric dyed with thecoupling product of diazotized3-chlor-6-methoxy-aniline and a non-substantive,n-auxochrome-substituted aceto-acetyl-anilide.

10. A cellulosic fabric dyed with the coupling product of2-methoxy-4-chloro-5-methyl-l-acetoacetanilide and the diazo-compound of1- ,amino-2-methyl-5schiorobenzene.

14. Fiber dyed with a water-insoluble coupling product of2-methoxy-4-chloro-5-methyl-l-acetoacetanilide and the diam-compound oflv ,mhIlhG ZQniethM-chIOrobenzehe." a

rial which comprises impregnating. the material with a basic pastecontaining a non-substantive, diazotized arylamine, having between oneand three n-auxochromesubstituents, which is stabilized by connection tothe nitrogen group of piperidine-alpha-carboxylic acid, and anon-substantive, aceto-acetyl-anilide having not more than threen-auxochrome substituents and being capable of forming with thediazotized arylamine an azo color, subjecting the impregnated materialat elevated temperature to the action of a mild acid, and washing anddrying the material.

17. The method of dyeing a cellulosic material which comprisesimpregnating the material with a basic paste containing anon-substantive, watersoluble diazo-amino derivative of an arylaminehaving one or more n-auxochrome substituents,

and a. non-substantive aceto-acetyl-anilide having not more than fiven-auxochrome substituents, subjecting the impregnated material atelevated temperature to the action of a mild acid, and washing thematerial. 18. The method of dyeing a cellulosic material .whichcomprises impregnating the material with 'a basic paste containing anon-substantive, watersoluble diazo-amino derivative of an arylaminehaving an n-auxochrome substituent, and a nonsubstantiveaceto-acetyl-anilide which may have an n-auxochrome substituent,subjecting the impregnated material at elevated temperature to theaction of a mild acid, and removing .inactive matterjrom the material. 1

19. The method of dyeing which comprises impregnating the material withacellulosic materiala basic pastecontaining a non-substantive, water- Isoluble diazo-amino derivative of an 'arylamine having an n-auxochromesubstituent, and a nonsubstantive aceto-acetyl-anilide which may have ann-auxochrome substituent, and subjecting the impregnated material atelevated temperature to the action of a mild acid. 1

20. The method of dyeing a cellulosicmaterial which comprises printingthe material with a paste containing'3.4 parts of 3-chlor-6'-methox yaniline stabilized by connection to the nitrogen group ofpiperidine-aJpha-carboxylic acid, 2.6 parts'ofaceto-acetyl-i-ethoxy-aniiine, 6.0 parts of the mono-ethyl-ether ofdiethylene-glycol, 2.0

parts of 26% sodium hydroxide solution, 36 parts of water at 140 F.,parts of starch-gum tragacanth thickener containing starch, gum, andwater in proportions of 80 parts of wheat starch,- 18 parts ofgumtragacanth (added as 360'parts of a 5% solution) and 560 parts of water;drying the impregnated material, exposing the material for about one andone-quarter minutes to the vapors of a'boiling 5% solution of aceticacid. rinsing with water, soaping, rinsing, and drying.

21. The method of dyeing a cellulosic material which comprises printingthe material with a aceto-acetyl 'l ethoxy-aniline 6.0 parts oftheethyl-ether of diethylene-glycol, 2.0-parts-of 26% sodium hydroxidesolution, 36 parts of waterat 140 F., 50 parts of starch-gum tragacanththickener containing starch,- gum, and water in proportions of 80.partsof wheat starch. 1a m v0126 1, sodium hydroxide aoiutlon, a thickener,of gum tragacanth (added as 360m of a 5% I andaaolvent.

muss A. mm.

solution) aqd '560 parts of water.

23. A composition of matter containing 3.4 FRII'HJOF ZW'ILGMEYER. partsof stabilized S-chlor-B-methoxy-anlllne, 2.8 ROBERT F. DEESE, JR. 5

NEWELL M. BIGELOW.

pgrts ot'aceto-acety1-4-ethoxy-anfl1ne, 2.0 parts

